CH655092A5 - METHOD FOR PRODUCING BRANCHED POLYCATIONIC CONNECTIONS. - Google Patents

Description

The present invention relates to processes for the preparation of compounds containing a plurality of quaternary ammonium groups.

DE-OS 1 795 392 discloses bifunctional compounds of the formula (I)

Z CH;

f1

■ N if A®

-Y-

R2 AV

©

CHjj-Z

(I)

wherein

Z CH2-CH-, CH2Cl-CHOH- or CH2Br-CHOH-,

\ /

O

R.! and R2 independently of one another alkyl (Ci_5) or hydroxyalkyl (C2_5),

Y alkylene (C2_ «), 2-hydroxy-1,3-propylene, -CH2CH2NHCONHCH2CH2- or -CH2CH2CH2NHCONHCH2CH2CH2-

Ae an anion and x 0 or an integer from 1 to 7, where if X = 2 or greater than 2, the individual meanings of Y are independent of one another.

According to DE-PS 1 795 392, the compounds of formula (I) are used to produce crosslinked polyamide amines by reaction with secondary amides.

DE-OS 3 111 386 describes the reaction of compounds of the formula (I) in which Z is CH2Cl-CHOH- or CH2Br-CHOH- with mono- or bifunctional amines, linear compounds being obtained, which in particular as Flocculants and emulsion calculating agents can be used.

It has now been found that branched compounds can be prepared by reacting polyfunctional amines with compounds of the formula (I).

The present invention relates to processes for the preparation of new branched polycationic compounds, characterized in that an amine which contains at least three reactive amino groups with a compound of the formula (I) or with a reaction product of the compound of the formula (I) with a mono - or bifunctional amine, this reaction product having at least one group Z per molecule, or with one

Mixture of such compounds. The invention also relates to the compounds produced in this way.

Compounds according to the invention can be obtained by a plurality of reactions starting with the preparation of the “coupling component” of the formula (I). According to DE-PS 1 795 392, this coupling component is reacted by reacting a specific excess of epihalohydrin, preferably epichlorohydrin, with a molo nofunctional secondary amine, e.g. Dimethylamine or a bifunctional tertiary amine, e.g. Tetramethyläthy-lendiamin or a mixture of such compounds. In order to obtain the coupling component with halogen end groups, the amine should be at least partially in salt form 15; The free amine must be used to obtain epoxy end groups.

Monofunctional amines are those that have a single reactive amino group per molecule; this can be primary, secondary or tertiary. Bifunctional or 20 polyfunctional amines are analogously those with 2 or more non-quaternary amino groups per molecule, which can react with epoxy groups or halogen.

A coupling component with 2 reactive end groups can react with a mono- or polyfunctional amine. Reactions with monofunctional tertiary amines result in terminal quaternary ammonium groups which do not react any further. Analogously, ammonia or monofunctional primary or secondary amines result in cationic ammonium salt groups which only react with halogen when the corresponding amine group has been released. Reactions with binfunctional amines can be controlled by controlling the molar ratios of the starting materials in such a way that either free end groups corresponding to the coupling component or free amino groups are obtained in the reaction product. Bifunctional amines therefore primarily have the function of extending the reaction product by bridging, although, as mentioned, it can also form an end group.

40

Ammonia or a primary or secondary monofunctional amine can also be reacted with more than just one end group of a coupling component, provided that after the first stage of the reaction, the 45 amino group is released again by neutralization. A polyfunctional amine can also be used for chain extension if only two amino groups are capable of reacting under the given reaction conditions.

50 A polyfunctional amine with at least three reactive groups leads to chain branching of the reaction product. Chain branching is also obtained with bifunctional amines when an amino group of the bifunctional amine reacts twice with an end group of coupling component 55. Ammonia or a monofunctional primary amine can even react three times with a coupling component. The number of reactive groups in an amine thus corresponds to the number of coupling components with which it can react.

60 cross-linked products are obtained when both ends of the coupling component are reacted with polyfunctional amines. In the reaction product, end groups are preferably formed by ammonia or monofunctional amines and bridge members are formed by bifunctional amines 65 and branchings are brought about by polyfunctional amines.

Preferred compounds of the present invention correspond to the formula

655 092

-Rh9ch-

11

Oh

-ch-oh

-ch;

"B—)

—Ch9ch-k ài oh

■ V

(a®)

m

(il)

worm

Cp a remainder (a)

-CH;

r

?1

fi

C ç

-ch2-

wherein R 1, R 2, Y and x have the above meaning, B is a radical of the formula (III)

D 'together with the two N atoms shown, one or more ring systems consisting of 5- to 7-ring members which may be saturated or unsaturated or aromatic and may contain further nitrogen atoms,

R 'and d have the above meaning,' (a) p independently of one another 0 or 1 and q 0 or 1, where the radical B in the case p = q = o contains no cationic groups,

i5 Z 'independently of one another CH2-CH-, R8CH2-CHOH-

\ /

0

or a radical of the formula (VII)

-k r

(iii)

20IK R-

* © ■ N-

ch,

R '

-ch-

Oh

(VII)

r '

r '

25th

R 'independently of one another are hydrogen, alkyl (Ci_2o), alkenyl (C2_2o), hydroxyalkyl (C2_6), aralkyl or a radical of the formula (IV)

-CH - CH-

2 l

■ H

R5 independently of one another is hydrogen or methyl, n is an integer from 2 to 150, preferably 2 to 50, D alkylene (C2_20), or a radical of the formula (V)

Rg bromine or chlorine,

R independently of one another hydrogen, alkyl (C, _20), alkenyl (C2_20), hydroxyalkyl (C2_6), cycloalkyl (C3_g),

Phenyl, aralkyl, alkaryl or a radical of the formula (IV), 30 or two radicals R together with the nitrogen atom to which they are attached, a saturated or unsaturated 5- to 7-membered ring which may contain one or more oxygen or further nitrogen atoms and where appropriate (IV) has alkyl substituents in positions that are not adjacent to the quaternary nitrogen atom, or three radicals R with the nitrogen atom to which they are attached, a polycyclic ring, which may contain further oxygen or nitrogen atoms , or an aromatic ring system which can contain one or more further nitrogen atoms,

Z 'furthermore a radical of the formula (VIII)

- (ch,)

2 d

-No;

rl

■ (CH2) r

(v) 45

r '

ch,

R

I.

R '

ch 0h

(VIII)

e 1 to 5,

d and f are independently 2 to 5,

R6 is hydrogen, alkyl (Ci_6), hydroxyalkyl (C2.6), haloal- 50 kyl (C | _6) or a radical of the formula (b)

X is a radical of the formula (IX) r '

- (CH)

2 g

R,

(CH2) h ~

(b)

n- KA'3- (ch 2 ^.

55

r '

r '' ©

n-

I.

r '

(IX)

g and h independently of one another 0, 1, 2 or 3 R7 are a 5- to 7-membered ring system which can be wholly or partly unsaturated and which can be carbocyclic or a heterocycle containing oxygen and / or nitrogen, or 60

B furthermore a radical of the formula (VI)

(RnP * ■

t <CH2 »d"

(VI)

where each R ', e and f have the above meaning, where for e - 1:

A 'is a radical of the formula (X) or (XI)

- ^ CH2 ^ d — N—

Rg— # (R ') 2-

(X).

-fcH2 ^ r fp— R '-

(XI),

655 092

wherein the third bond represents an additional bond of the radical X, R9 alkylene (Ci_5), and for e> 1: each A 'independently of one another a radical of the formulas (X), (XI) or (XII)

—Fch ^ NR1 -

(XII)

where not all A 'is a radical of the formula (XII), or X is a radical of the formula (XIII)

R '

1®-

R1

Q is a 3- to 7-valent hydrocarbon radical, or X is a 3-fold or 4-fold substituted radical of hexamethylene tetramine

k 0 or an integer of preferably 1 to 10, preferably 0 or an integer of 1 to 5, preferably Ooderl,

y is an integer from 3 to 7, preferably 3 or 4 Ae an anion,

m is an integer equal to the number of cationic

Mean places in the molecule.

The molar ratios of the reaction components are preferably such that at least 1 mol of the compound of the formula (I) is used per mole of the polyfunctional amine in order to obtain sufficient branching, the remaining end groups Z optionally being reacted with further, preferably monofunctional amine. In this sense, the molar ratios are calculated in a known manner in such a way that the desired branching is obtained and end groups Z are subsequently reacted, if appropriate.

It goes without saying that the same number of cationic and anionic groups are present in each compound, even if the anion, e.g. is not expressly stated in rest A. In many cases, the specification of the anion is omitted for the sake of simplicity. All symbols that appear more than once in a formula generally have an independent meaning, unless the opposite is determined.

In the rest Cp mean R! and R2 preferably methyl and x independently of one another zero or 1, preferably 1 and y 2-hydroxy-1,3-propylene.

B preferably denotes a radical of the formula (III) in which R 'independently of one another is hydrogen or methyl and D preferably D ", ie alkylene (C2_] 2), preferably -C2H4-, {CH2) -6 or -fCH ^ or a radical of the formula (V) in which e = 1, d and f independently of one another are preferably 2 or 3 and Rg is hydrogen.If B is a radical of the formula VI, D 'together with the two nitrogen atoms preferably forms a piperazine ring, where p = 1, R 'is hydrogen, d = 2 and q = 0 or 1.

Of the radicals of the formula (III), preference is further given to those where one R 'is alkyl (C8-20), preferably alkyl (Cu_15) and the other three R' are hydrogen, and D has the meaning given above for D ".

5 Z 'preferably denotes a radical of the formula (VII). Preferred radicals are those in which all the substituents R are different from hydrogen and are preferably alkyl (Ci-2o) or hydroxyalkyl (C2_6). Preferred are those in which either all substituents R hydroxyal-10 kyl (C2_4), in particular hydroxyethyl, or one R alkyl (Q-ib), in particular alkyl (Cio_14), and the other two R alkyl (Ci_4), preferably methyl, or hydroxyalkyl (C2 ^), preferably hydroxyethyl.

Z 'furthermore preferably denotes those radicals of the formula (VII) in which 1 or 2 substituents R are hydrogen and the other R are alkyl (Ci_20), hydroxyalkyl (C2_6) or benzyl. In particular, radicals Z' are preferred which have at least one Have alkyl (Cg_i8) group, such as Derivatives of coconut or hardened tallow fatty acid 20 amines.

Each molecule contains the same number of anion equivalents as cationic groups. The nature of the anion is not critical, but the anion which is preferably used is that which appears in the end product 25 as a result of the reaction products, ie Cle when reacting with epichlorohydrin. However, the anion can also be exchanged in part with another desired anion using methods known per se.

The symbol Ae stands for an anion equivalent, such as 30 for a polyvalent anion S04ee, for '/ 2 S04ee

In the case of the cationic groups, a distinction must be made between quaternized and protonated cationic groups. Treating a protonated cationic group with base 35 transforms it into a secondary or tertiary amine group. Of course, this results in differences in the acid / base function and the water solubility of the compound and, in relation to the protonated compounds, provides further reactive groups which can be reacted with the coupling component.

According to the invention, the end products can be produced in a very targeted manner by precise control of the starting materials, their molar ratios in each process stage, the reaction conditions, such as the temperature or the pH.

The properties of the compounds of the formula (II) depend above all on the chain length, their branching and crosslinking, the cationic groups and the nature of the substituents. So it is e.g. possible to make the compound of For-50 mei (II) water-insoluble by introducing a relatively large number of lipophilic residues, while on the other hand the compound of formula (II) will generally be water-soluble in the case of short-chain substituents. Various amines of the formulas (IX, X and XI) can of course also be reacted with the coupling component in accordance with the properties which the end product is to have.

The compounds of the formula (II) are particularly valuable for use as flocculating agents or as emulsifying agents for oil-in-water or water-in-oil emulsions.

The reaction conditions for the preparation of the compounds according to the invention depend both on the desired end product and on the properties of the starting materials or, in the case of a gradual build-up, on those of the intermediates. If reactive amines are used, the reaction is generally exothermic, even if the coupling component is in aqueous

ger solution is available. In this case, the reaction can be controlled by slowly adding a reaction partner, the reaction possibly being kept under control by additional cooling. The initial temperatures are usually between 0 and 100 ° C, preferably 20 to 60 ° C. The upper temperature limit depends largely on the boiling point of the amine used and on the desired end product. In certain cases, one or the other reaction component or both may be in aqueous solution or may be reacted in the presence of water. In other cases, the absence of water will be beneficial or necessary. However, organic solvents, preferably polar organic solvents, can also be used for the reaction.

If the coupling component contains epoxy end groups, they only react with tertiary amines in the presence of proton donors, e.g. protonated tertiary amines. The reaction is preferably carried out in a slightly acidic medium or in a proton-donating solvent. The coupling component preferably contains halogen end groups and the reaction conditions are weakly acidic to neutral.

Amines with low reactivity or low water solubility usually require careful control of the pH during the reaction. A polar solvent is usually advantageous for good distribution in the reaction medium. It will usually be convenient to mix the reaction components at room temperature and start the reaction by increasing the temperature. For inert amines, the reaction temperature will generally be higher than for more reactive ones. These factors also influence the choice of the most suitable solvent, the boiling point of which should be at least as high as the reaction temperature. The reaction temperature is usually between 60 and 100 ° C. Suitable solvents are e.g. lower alcohols, e.g. Ethanol or n- or isopropanol, glycols, such as ethylene glycol or their ether. If desired, the solvent can be distilled off or, in the case of a gradual reaction, can remain in the reaction mass or possibly. form a component of the end product. The control of the course of the reaction can e.g. by measuring the consumption of the amine or the coupling component, using known analytical methods.

The following examples illustrate the invention. Parts mean parts by weight and degrees Celsius degrees.

Example aj-c): Production of a coupling component. Example a): Coupling component with halogen at the end.

882 parts of 30% hydrochloric acid are slowly added dropwise to a mixture of 3514 parts of deionized water and 1131 parts of a 60% dimethylamine solution, the temperature being kept at 35-40 °. 2093 parts of epichlorohydrin are now slowly added to the mixture with stirring. The temperature is kept at 35-40 ° by cooling. After the addition has ended, the mixture is left at this temperature for a further 8 hours and then cooled to room temperature. A 3: 2 addition product is obtained which contains 2 anion-equivalent chloride and 2 mol of non-ionic active chloride per mol of reaction product.

Example b)

104.3 parts of 35% aqueous hydrochloric acid are slowly added to 150 parts of 60% aqueous dimethylamine with stirring and cooling so that the temperature does not rise above 40 °. Finally, 277.5 parts of epichlorohydrin

7 655 092

slowly added at a temperature of 35-40 °. The reaction mixture is stirred for a further hour at 50 ° and left to stand overnight.

s Example c): Coupling component with terminal epoxy groups.

50 parts of water are added dropwise with cooling to 50 parts of tetramethylethylenediamine. Finally, 79.8 parts of epichlorohydrin are added at such a rate that the reaction temperature is kept at 35-40 °. After adding about 25% of the total amount of epichlorohydrin, the reaction mixture becomes viscous and cloudy. Another 80 parts of water are added so that the reaction mixture is clear and diluted. The addition of Epi-i5 chlorohydrin is now continued for 2-3 hours until the end. The reaction mass is then heated to 40 ° for 2 hours and to 60 ° for a further 2 hours.

Examples 1-3, branching reactions. 20 Example 1

103 parts of diethylenediamine are added to the reaction mixture obtained in Example a) at a temperature of 85 ° over a period of 1 hour. The reaction mixture is kept at 90 ° for 18 hours until analysis 25 shows a maximum content of anionic chloride and thus also an increased degree of branching.

Example 2

140 parts of a 25% strength aqueous solution of hexamethylenetetramine are added dropwise to the aqueous reaction mixture obtained in Example 30 b) at 70 ° over 30 minutes. The reaction mixture is then heated to 95 ° for 2 hours and left at this temperature for a further 4 hours, the anionic chloride content reaching a maximum.

Example 3

25 parts of tetraethylene pentamine are slowly added to 400 parts of the aqueous solution obtained according to Example a) at 90 °. The reaction mixture is left at 90 ° until the anionic chloride content reaches a maximum. A branched, fully reacted product is obtained.

4S example 4

The product obtained according to Example 3 is mixed with 90 parts of triethanolamine at 90 ° for 1 hour. The reaction mixture is left at this temperature until the reaction has ended. The reactive end groups of the starting material are now completely implemented with triethanolamine.

Example 5

The product obtained in Example 3 is stirred at 30 ° 55 and mixed with 19.2 parts of a 35% aqueous ammonia solution over an hour. The reaction mixture is stirred for a further hour at 50 °, the reaction then being complete.

60 Example 6

14.8 parts of a 60% aqueous dimethylamide solution are added to the product from Example 3 with stirring at 40 ° over a period of one hour. The mixture is stirred at 60 ° for a further hour, the 65 reaction having ended.

Example 7

The product from Example 3 is stirred at 70 ° and with

655 092

42.2 parts of a dimethylalkylamine mixture were added over 30 minutes. This amine mixture contains amines of the formula

RcN (CH3),

where Rc is alkyl with the following composition:

Alkyl C6 0.5 parts; (C8): 0.8 parts; (CI0): 7.0 parts; (CI2): 50.0 parts; (C14): 18.0 parts; (CI6): 8.0 parts; (CI8): 1.5 parts.

8th

The reaction is held at 70 ° for a further hour, then heated to 90 ° and stirred for a further 4 hours. A clear product is obtained. The products of Examples 1-7 can be used in concentrations of 5,500-5,000 ppm to break oil in water emulsions, such as, for example, oil-contaminated wastewater or waste from grease and oil-containing coolants / lubricants in the metal industry.

10th

C.

Claims (10)

655 092 1. A process for the preparation of branched polycationic compounds, characterized in that an amine containing at least three reactive amino groups with a compound of formula (I) or with a reaction product of the compound of formula (I) with a mono - or bifunctional amine, this reaction product having at least one group Z per molecule, or reacting with a mixture of such compounds of the formula (I), these compounds of the formula z CH; Î1 N © r2 Ä L © r2 ä 0 correspond to what Z CH2-CH-, -CHOH-CH2Cl or -CHOH-CH2Br, \ / O CH — Z (I) R] and R2 independently of one another alkyl (Q.s) or hydroxyalkyl (C25), Y alkylene (C2 6), 2-hydroxy-l, 3-propylene, -CH2CH2NHCONHCH2CH2- or 15 -CH2CH2CH2NHCONHCH2CH2CH2-, Ae denotes an anion, and x denotes 0 or an integer from 1 to 7, where x = 2 or greater than 2, the individual meanings of Y are independent of one another, and if the compound of the formula 20 (I) contains epoxy end groups, the reaction with tertiary amines takes place in the presence of proton donors. 2. Compounds of formula (II) ■ CHpCH— c- CH — CH5 ß —— ch0CH c z ' P «<£ k àt P Oh oh oh (a0) m (II) wherein Cp a remainder (a) 30th -ch; h b r ir r, L CJ "CH ^ - 35 (a) -ch - ch 0- 2 d -NO; • (ch,) ZJf (V) f -te- I. r1 f " e 1 to 5, d and f are independently 2 to 5, R6 is hydrogen, alkyl (Cj_6), hydroxyalkyl (C2_4), haloalkyl (Ci_6) or a radical of the formula (b) 50 - (CH) - (III) 2 g Pv. (cVh " (b) g and h independently of one another 0, 1, 2 or 3 R7 is a 5- to 7-membered ring system which can be completely or ss partially unsaturated and which is carbocyclic in which R 'is independently hydrogen, alkyl (Ci_20), or an oxygen and / or Nitrogen-containing hetero-alkenyl (C2_20), hydroxyalkyl (C ^), aralkyl or a radical cyclus, or B furthermore a radical of the formula (IV) (VI) (R ') ^ - © - : r "). % ■ (CH,) Z'd r ' 11 © (VI) 2 i r5 _j h (IV) n R5 is independently hydrogen or methyl, n is an integer from 2 to 150, 40 D alkylene (C2_2o) or a radical of the formula (V) wherein Rls R2, Y and x have the meaning given in claim 1 under formula (I), B a radical of the formula (III) 45 "(ch,) 3. Compounds of formula (II) according to claim 2, wherein R] and R2 are methyl, x zero or 1 and Y is 2-hydroxy-1,3-propylene. 3rd 655 092 D 'together with the two N atoms shown, one or more ring systems consisting of 5 to 7 ring members which may be saturated or unsaturated or aromatic and may contain further nitrogen atoms, R 'and d have the above meaning, p independently of one another 0 or 1 and q 0 or 1, where the radical B in the case p = q = 0 contains no cationic groups, Z 'independently of one another CH2-CH-, R8CH2-CHOH- \ / O or a radical of the formula (VII) ("CH 2" hj -NR '(XII), where not all A 'is a radical of the formula (XII), or s X is a radical of the formula (XIII) r' 10, K \ ® r n — ch, r ^ r ' (XIII) ■ ch - Oh (VII) Rg bromine or chlorine, R independently of one another hydrogen, alkyl (C] _20), alkenyl (C2.20), hydroxyalkyl (C2_6), cycloalkyl (C3 8), Phenyl, aralkyl, alkaryl or a radical of the formula (IV), or two radicals R together with the nitrogen atom to which they are attached, a saturated or unsaturated 5- to 7-membered ring which may contain one or more oxygen or further nitrogen atoms and which optionally has alkyl substituents in positions which are not adjacent to the quaternary nitrogen atom, or three radicals R with the nitrogen atom to which they are attached, a polycyclic ring which may contain further oxygen or nitrogen atoms, or an aromatic ring system which has one or can contain several more nitrogen atoms, Z 'furthermore a radical of the formula (VIII) Q is a 3- to 7-valent hydrocarbon radical, or X is a 3-fold or 4-fold substituted radical of hexamethylene tetramine 20th 25th ch; i ® "n -I ch " ch, ch ^ nvCH, r 'r' n d ß- ch, r 'r' X is a radical of the formula (IX) ■ ch— (VIII) oh r 'r' '©' © -n [a '] - (ch2) f n - r 'r' wherein each R ', e and f have the meaning given above, where for = 1: A' is a radical of the formula (X) or (XI) -4ch2 -ys— n - 3o k 0 or an integer from 1 to 10, y is an integer from 3 to 7, Ae an anion, m is an integer equal to the number of cationic sites in molecule 35. 4. Compounds of formula (II) according to Patent claims 4o chen 2 and 3, wherein B is a radical of formula (III), wherein R ' independently of one another hydrogen or methyl or D = D ", i.e. alkylene (C2_i2) or a radical of the formula (V) in which e = 1, d and f independently of one another mean 2 or 3 and R6 is hydrogen. 45 5. Compounds of formula (II) according to claims 2 and 3, wherein B is a radical of formula VI, wherein D 'together with the two nitrogen atoms represents a piperazine ring and p = 1, R' is hydrogen, d = 2 and q = 0 or 1 means. so 6. Compounds of formula (II) according to claims 2-5, wherein Z 'is a radical of formula (VII), in which all the substituents R are different from hydrogen and are alkyl (Ci_2o) or hydroxyalkyl (C2_.6). 7. Compounds of formula (II) according to patent claims (x), 55 chen 2-6, wherein X is a radical of the formula (IX) rg — iß (r ') 2- 60 _4ch2 —rp r ' I. (xi), r ' -ißL I. r ' r ' -4CH2> d 4ch2) -f - r ' Jp— I. r ' the third bond being an additional bond of the radical X, R9 alkylene (C! _5), and for> 1: each A 'independently of one another a radical of the formulas (X), (XI) or (XII) wherein R 'independently of one another are hydrogen, alkyl (Cj_4) 65 or -CH2-CH2OH, d and f are independently of one another 2 or 3 and e is 1 ^ 4. 8. Compounds of formula (II) according to claim 7, wherein X 655 092 <±> 0 © -NH2-CH2-CH2-NH-CH2-CH2-NH2-I means. 9. Compounds of formula (II) according to claims 2 to 6, wherein X is tri- or tetrasubstituted hexamethyl-lentetramine. 10. Use of the compounds of formula (II) according to one of claims 2 to 9 for breaking oil-in-water or water-in-oil emulsions by adding such a compound to such an emulsion.